CA1259184A - Corrosion inhibiting coating compositions - Google Patents
Corrosion inhibiting coating compositionsInfo
- Publication number
- CA1259184A CA1259184A CA000505149A CA505149A CA1259184A CA 1259184 A CA1259184 A CA 1259184A CA 000505149 A CA000505149 A CA 000505149A CA 505149 A CA505149 A CA 505149A CA 1259184 A CA1259184 A CA 1259184A
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- CA
- Canada
- Prior art keywords
- inorganic oxide
- composition
- corrosion
- coating composition
- corrosion inhibiting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
CORROSION INHIBITING COATING COMPOSITION
A composition suitable for the preparation of a surface protective coating composition eg a paint by admixture with an organic film-forming binder comprises (i) elemental zinc in particulate form and (1i) inorganic oxide particles such as silica having corrosion inhibiting cations eg calcium chemically bound to the surface by ion exchange. The amount of elemental zinc to inorganic oxide is preferably from 75:1 to 3:1 by weight. The binder can be organic eg an epoxy resin, epoxy ester, chlorinated rubber or polystyrene or may be inorganic eg silicates.
CORROSION INHIBITING COATING COMPOSITION
A composition suitable for the preparation of a surface protective coating composition eg a paint by admixture with an organic film-forming binder comprises (i) elemental zinc in particulate form and (1i) inorganic oxide particles such as silica having corrosion inhibiting cations eg calcium chemically bound to the surface by ion exchange. The amount of elemental zinc to inorganic oxide is preferably from 75:1 to 3:1 by weight. The binder can be organic eg an epoxy resin, epoxy ester, chlorinated rubber or polystyrene or may be inorganic eg silicates.
Description
~2~
Case6067(23 CORROSION INHIBITING COATING COMPOSITIO~
The prese~t invention relates to a composition su~table for the preparation of a surface protective coating composition by admixture with a binder, to a coating compo ition 50 prepared for inhibiting corrosion of metal surface~ particularly ferrous metal surface3 and to articles or structures having ferrou~ metal ~urfaces coated with such a composition.
It is well known that a ~etal surface can be protected agaillst corroslon by placing in electrical contact with the metal ~urface a second metal of lower standard elec~rode potential (i.e~ a sacrificial netal)~ A common e~ample of this for~ of protection is galvanised steel.
The usa of sacrificial ~etal partlcles, usually finely divided particle~, in paints is al~o known~ In particular, it ls known to protect steel surfaca3 with paint containing zinc dust. The known zinc-containing paints may contaln orgsnlc or inorganic binders such as, for example, epoxy resins or ethyl ~illcate. Generally the zinc content of such paint~ is from 70 to 95 per cent by weight and the paints are therefore commonly known as zlnc-rich paints.
~inc-rich paint~ can provide very good corrosion protection to steel surfaces. However, if left exposed to the environment, a layer of whlte zinc corroslon products forms relatively quickly on the ~urface, These corrosion deposlts are unsightly ~nd make further coating difficult. ~ven ~hen the zinc-rich coatings are provided wi~h an overcoat of another palnt prior to expo3ure to the en~ironment3 inc corrosion may cau~e intercoat adhesion problems ~o snd the white zlnc corro~io~ product~ may stlll be depo~ited o~ the ~rface.
It ha3 now been found that the problzms a~sociated with the zinc corro~lo~ in zinc-rlch coating composltio~s may be reduced by the inclu~lon in the co~po~ition of an effective amount of inorganic oxide particle~ having corrosion inhlbl~ing ions chemlcally bound to the ~urface of the inorganlc oxide particle~ by ion-excbange.
Accordlng to one aspect of the present inv~ntion a composition ~uitable for the preparatlon of a surface protective coating composltloa by adml~ture with a blnder~ comprise~:
(i) elemental zinc ln particulate form, (ii~ lnorganic oxide particle~ ha~ing corro3ion lnhibiting ca~ion~
che~lcally bound to the surface thereof by ion exchange.
The amoune of elemental ~inc to ion exchanged inorganic o~ide 15 i8 preferably from 75:1 to 3:1 by weight.
According to another a~pect of the present invention a coa~lng CompO~itiQn 3uitable for appllcation eo a metal surface to Inhlblt corrosion (i) a binder, (ii) from 50 to 90% by weight of elemental zinc in part~cula~e for~
based on the welgh~ of the coating compo3ition, and (lii) an effec~i~e æmount of inorganlc oxlde particles having corro~ion inhlbiting ion~ chemically bound to the surface therPof by ion-e~change.
The amount o~ binder can conveniently be in ~he range 10 to 60%
preferably 15 to 35Z by weight bs~ed on the weight of the coating co~po~itlon.
Inorganic o~ide particleY having corrosion inhibiting io~s bound to the aurfsce of the lnorganic oxide partlcles by ion-exchange are know~ a~ corro~ion inhibitors and are di~clo~ed ln UX Patent GB 2071070B, European Patent Appllcatlon 46057 and ~uropean Paten~ Appllcation 89810. Britlsh Patent Application 2091235 discloses a method of preparing certain corro~lon inhibitor3 of thl~ type.
~, ~, ~259~
Any o~ the ion-exchanged inorganic oxide particles disclosed in these patents and patent application3 may be used in the present invention. However, the preferred particles are tho3e in which the ions bound to the inorganic oxide are cations and the preferred inorganic oxide i9 silica.
Particularly preferred for use in the pre~ent invention is a corroslon inhibitor conprising silica particles having calcium ions chemically bound to the particle~ of the silica by ion-exchange.
The inorganic oxide particles preferably have a particle slze of less than 40 microns, more preferably less than 25 microns.
The inorganlc oxide can conveniently contain up to 2.5 millimoles/g of corrosion iahibiting ion~. The lower limit can be about 0.01 milllmoles/g but is preferably 0.05 millimoles/g.
Typically, the total amount of the elemental zinc and ion-exchanged inorganic oxide contained in the coating conpositlon is from 60 to 95% by welght. The volume ratio of ~inc to ion~exchanged inorganic oxide may be, for example, from 1:0.05 to 1:1.2 preferably 1:0.67 to 1:1 or on a weight basis from 75:1 to 3:1.
Typically the coating composition of the invention will contain a binder for the zinc and inorganic oxide particles, particularly a film-forming polymer particularly an organic polymer or resin binder. Examples of organic binders include epoxy resins, epoxy esters, chlorinated rubber and polystyrene. Inorganic binders include silicates (both organic and inorganic).
The coating composltion may be in the form of a paint by which we mean to include enamels, lacquers, varnishes, undercoats, primers, seals, fillers, stoppers and the like.
The coating composition can include a solvent.
The coatlng composltion may also contain additives conventionally used in paints such as, for example, pigments, driers, thlckeners and anti-skinning agents.
The coating composition5 may be prepared and applied by conventional techniques.
The pre~ent invention includes structures coIprising a ~25~
ferrous metal surface provided with a costing accordlng eo the present invention.
The invention is lllustratPd by the following examples.
Example 1 Preparation of Calcium Exchan~ed Silica Calcium hydroxide was 810wly added to a stlrred slurry of silica in water (one part by weight of 3ilica to two parts by weight of water) at room temperature, i.e~ about 20~C. The pH was not allo~ed to rise above 10. Once the pH was ~table, the calcium exchanged silica was filtered, washed and milled in water. The product was then dried on trays in an oven. X-ray fluorescence analysis of the product lndicated a calcium co~tent of 6.6% by weight (1.65 ~illlmoles/g?. The mean particle size was 7.1 microns.
Pre~aration of Paint A zlnc-rich paint according to the present lnvention having the composition given in Table 1 was prepared by mixing approximately one third of the resln with all of the other components, except the drier, for 20 hours in a ball mill and then blending in the remaining resln and drler.
For comparison a similar zinc-rich paint composition, not according to the present invention, which contained no calcium-exchanged sil~ca was prepared. The comparative composition is also given in Table 1 ~259~
Table 1 - Pain~ Composition~
_ ~ .
Component (% by weight) Example 1Comparative Compositio~ A
. . _ _ Air drying epoxy ester resin 11.58 10.98 (Synolac 463X ex Cray Valley Products) as Binder Zinc Dust 72.10 75.95 Calcium-e~changed silica 2.17 Calcium oxide as water scavenger 0.52 0.50 Bentone 34 0074 0.70 Methanol (Activator for Bentone 0.22 0.20 10% cobalt octoate (drler) 0.33 0.03 ~ex Manchem Ltd) Xylene as solvent 12.64 11.64 _ _ _ *Pigment Volume Concentration (%~ 65.4 65.4 Specific Grsvity of the liquid 2.55 2.72 Volume Solids % in the liquid 48.6 49.1 paint "Synolac" is a registered ~rade mark * refers to all aolids except the epoxy ester resin and is ~he volume concentratlon in the dry film.
Bentone 34 is a commeric~lly available organlc modified montmorillonite clay sold by NL Industries and i~ used as a gelling agent and rheology modifier. BENTON~ is a registered trade mark.
Corrosion Test The paint compo~ltions were applied to standard degreased, polished mild steel plates by brush coatlng and allowed to dry. The dry film thickness of the palnts was from 85 to 105 micrometre~.
The coating~ were scribed through to the bare metal and the panels subJected to the ASTM B117-73 salt spray test. After 24 hour3 exposure to the salt spray~ the panel coated with the comparative composition had white zinc corrosion deposits over its entire surface whereas the panel coated with the composltion according to the present invention wa~ free of such corrosion products. After 350 hours exposure to the salt spray, the panel coated with the comparative composltion had relatively large amounts of white zinc corrosion deposits on the surface, the coating wa~ blistered and corrosion of the metal surface waB evident. The panel coated with the paint according to the present invantion had, after 350 hours, only small amounts of the white zinc corrosion deposits on the surface. There was no blistering of the paint film and no evidence of corrosion of the mild steel.
These .esults show by use of the invention:
(i) the amount of white zinc corrosion deposits on the surface is greatly reduced, and (li) the corrosion of the steel i8 al30 reduced.
Example 2 Preparation of Calcium Exchan~ed Silica Calcium exchanged silica was prepared as described 1n Example l except that the product was dried by heating the filter cake in an oven and was micronised to a mPan particle size of 4.3 microns after drying. X-ray fluorescence analys~s of the product lndicated a calcium content of 6.1% by weight (1.55 millimoles/g).
Preparation of Paint Five zinc-rich paint composltlons according to the present invention were prepared containing different quantities of the calcium-exchanged silica corro~ion inhlbiting particlesO The compositions of these five paints are glven ln Table 2 together with the compositions of two comparative compositlons.
~:~5~
Table 2 - Paint Co~positions _ _ _ Parts by welgh _ 5 Gomponent Comparative Examples Composit~ons _
Case6067(23 CORROSION INHIBITING COATING COMPOSITIO~
The prese~t invention relates to a composition su~table for the preparation of a surface protective coating composition by admixture with a binder, to a coating compo ition 50 prepared for inhibiting corrosion of metal surface~ particularly ferrous metal surface3 and to articles or structures having ferrou~ metal ~urfaces coated with such a composition.
It is well known that a ~etal surface can be protected agaillst corroslon by placing in electrical contact with the metal ~urface a second metal of lower standard elec~rode potential (i.e~ a sacrificial netal)~ A common e~ample of this for~ of protection is galvanised steel.
The usa of sacrificial ~etal partlcles, usually finely divided particle~, in paints is al~o known~ In particular, it ls known to protect steel surfaca3 with paint containing zinc dust. The known zinc-containing paints may contaln orgsnlc or inorganic binders such as, for example, epoxy resins or ethyl ~illcate. Generally the zinc content of such paint~ is from 70 to 95 per cent by weight and the paints are therefore commonly known as zlnc-rich paints.
~inc-rich paint~ can provide very good corrosion protection to steel surfaces. However, if left exposed to the environment, a layer of whlte zinc corroslon products forms relatively quickly on the ~urface, These corrosion deposlts are unsightly ~nd make further coating difficult. ~ven ~hen the zinc-rich coatings are provided wi~h an overcoat of another palnt prior to expo3ure to the en~ironment3 inc corrosion may cau~e intercoat adhesion problems ~o snd the white zlnc corro~io~ product~ may stlll be depo~ited o~ the ~rface.
It ha3 now been found that the problzms a~sociated with the zinc corro~lo~ in zinc-rlch coating composltio~s may be reduced by the inclu~lon in the co~po~ition of an effective amount of inorganic oxide particle~ having corrosion inhlbl~ing ions chemlcally bound to the ~urface of the inorganlc oxide particle~ by ion-excbange.
Accordlng to one aspect of the present inv~ntion a composition ~uitable for the preparatlon of a surface protective coating composltloa by adml~ture with a blnder~ comprise~:
(i) elemental zinc ln particulate form, (ii~ lnorganic oxide particle~ ha~ing corro3ion lnhibiting ca~ion~
che~lcally bound to the surface thereof by ion exchange.
The amoune of elemental ~inc to ion exchanged inorganic o~ide 15 i8 preferably from 75:1 to 3:1 by weight.
According to another a~pect of the present invention a coa~lng CompO~itiQn 3uitable for appllcation eo a metal surface to Inhlblt corrosion (i) a binder, (ii) from 50 to 90% by weight of elemental zinc in part~cula~e for~
based on the welgh~ of the coating compo3ition, and (lii) an effec~i~e æmount of inorganlc oxlde particles having corro~ion inhlbiting ion~ chemically bound to the surface therPof by ion-e~change.
The amount o~ binder can conveniently be in ~he range 10 to 60%
preferably 15 to 35Z by weight bs~ed on the weight of the coating co~po~itlon.
Inorganic o~ide particleY having corrosion inhibiting io~s bound to the aurfsce of the lnorganic oxide partlcles by ion-exchange are know~ a~ corro~ion inhibitors and are di~clo~ed ln UX Patent GB 2071070B, European Patent Appllcatlon 46057 and ~uropean Paten~ Appllcation 89810. Britlsh Patent Application 2091235 discloses a method of preparing certain corro~lon inhibitor3 of thl~ type.
~, ~, ~259~
Any o~ the ion-exchanged inorganic oxide particles disclosed in these patents and patent application3 may be used in the present invention. However, the preferred particles are tho3e in which the ions bound to the inorganic oxide are cations and the preferred inorganic oxide i9 silica.
Particularly preferred for use in the pre~ent invention is a corroslon inhibitor conprising silica particles having calcium ions chemically bound to the particle~ of the silica by ion-exchange.
The inorganic oxide particles preferably have a particle slze of less than 40 microns, more preferably less than 25 microns.
The inorganlc oxide can conveniently contain up to 2.5 millimoles/g of corrosion iahibiting ion~. The lower limit can be about 0.01 milllmoles/g but is preferably 0.05 millimoles/g.
Typically, the total amount of the elemental zinc and ion-exchanged inorganic oxide contained in the coating conpositlon is from 60 to 95% by welght. The volume ratio of ~inc to ion~exchanged inorganic oxide may be, for example, from 1:0.05 to 1:1.2 preferably 1:0.67 to 1:1 or on a weight basis from 75:1 to 3:1.
Typically the coating composition of the invention will contain a binder for the zinc and inorganic oxide particles, particularly a film-forming polymer particularly an organic polymer or resin binder. Examples of organic binders include epoxy resins, epoxy esters, chlorinated rubber and polystyrene. Inorganic binders include silicates (both organic and inorganic).
The coating composltion may be in the form of a paint by which we mean to include enamels, lacquers, varnishes, undercoats, primers, seals, fillers, stoppers and the like.
The coating composition can include a solvent.
The coatlng composltion may also contain additives conventionally used in paints such as, for example, pigments, driers, thlckeners and anti-skinning agents.
The coating composition5 may be prepared and applied by conventional techniques.
The pre~ent invention includes structures coIprising a ~25~
ferrous metal surface provided with a costing accordlng eo the present invention.
The invention is lllustratPd by the following examples.
Example 1 Preparation of Calcium Exchan~ed Silica Calcium hydroxide was 810wly added to a stlrred slurry of silica in water (one part by weight of 3ilica to two parts by weight of water) at room temperature, i.e~ about 20~C. The pH was not allo~ed to rise above 10. Once the pH was ~table, the calcium exchanged silica was filtered, washed and milled in water. The product was then dried on trays in an oven. X-ray fluorescence analysis of the product lndicated a calcium co~tent of 6.6% by weight (1.65 ~illlmoles/g?. The mean particle size was 7.1 microns.
Pre~aration of Paint A zlnc-rich paint according to the present lnvention having the composition given in Table 1 was prepared by mixing approximately one third of the resln with all of the other components, except the drier, for 20 hours in a ball mill and then blending in the remaining resln and drler.
For comparison a similar zinc-rich paint composition, not according to the present invention, which contained no calcium-exchanged sil~ca was prepared. The comparative composition is also given in Table 1 ~259~
Table 1 - Pain~ Composition~
_ ~ .
Component (% by weight) Example 1Comparative Compositio~ A
. . _ _ Air drying epoxy ester resin 11.58 10.98 (Synolac 463X ex Cray Valley Products) as Binder Zinc Dust 72.10 75.95 Calcium-e~changed silica 2.17 Calcium oxide as water scavenger 0.52 0.50 Bentone 34 0074 0.70 Methanol (Activator for Bentone 0.22 0.20 10% cobalt octoate (drler) 0.33 0.03 ~ex Manchem Ltd) Xylene as solvent 12.64 11.64 _ _ _ *Pigment Volume Concentration (%~ 65.4 65.4 Specific Grsvity of the liquid 2.55 2.72 Volume Solids % in the liquid 48.6 49.1 paint "Synolac" is a registered ~rade mark * refers to all aolids except the epoxy ester resin and is ~he volume concentratlon in the dry film.
Bentone 34 is a commeric~lly available organlc modified montmorillonite clay sold by NL Industries and i~ used as a gelling agent and rheology modifier. BENTON~ is a registered trade mark.
Corrosion Test The paint compo~ltions were applied to standard degreased, polished mild steel plates by brush coatlng and allowed to dry. The dry film thickness of the palnts was from 85 to 105 micrometre~.
The coating~ were scribed through to the bare metal and the panels subJected to the ASTM B117-73 salt spray test. After 24 hour3 exposure to the salt spray~ the panel coated with the comparative composition had white zinc corrosion deposits over its entire surface whereas the panel coated with the composltion according to the present invention wa~ free of such corrosion products. After 350 hours exposure to the salt spray, the panel coated with the comparative composltion had relatively large amounts of white zinc corrosion deposits on the surface, the coating wa~ blistered and corrosion of the metal surface waB evident. The panel coated with the paint according to the present invantion had, after 350 hours, only small amounts of the white zinc corrosion deposits on the surface. There was no blistering of the paint film and no evidence of corrosion of the mild steel.
These .esults show by use of the invention:
(i) the amount of white zinc corrosion deposits on the surface is greatly reduced, and (li) the corrosion of the steel i8 al30 reduced.
Example 2 Preparation of Calcium Exchan~ed Silica Calcium exchanged silica was prepared as described 1n Example l except that the product was dried by heating the filter cake in an oven and was micronised to a mPan particle size of 4.3 microns after drying. X-ray fluorescence analys~s of the product lndicated a calcium content of 6.1% by weight (1.55 millimoles/g).
Preparation of Paint Five zinc-rich paint composltlons according to the present invention were prepared containing different quantities of the calcium-exchanged silica corro~ion inhlbiting particlesO The compositions of these five paints are glven ln Table 2 together with the compositions of two comparative compositlons.
~:~5~
Table 2 - Paint Co~positions _ _ _ Parts by welgh _ 5 Gomponent Comparative Examples Composit~ons _
2 3 4 5 6 B C
_ _ _ _ Epoxy resin6.166,37 6.83 7O358.23 5.79 6.03 (Epicote 1001X75 ex SHELI.) 15 Beetle BE 640 0.41 0.42 0.450.49 0.7 0.38 0.40 (ex BP Chemicals Limited) Thi~omen 0.34 0.35 0.37 0.40 _ 0.32 0.33 20 (ex ICI) Zlnc Dust77.6075.74 71O61 66.84 61,2681.00 75.95 Calclum- 2.16 3.36 5.99 9.0512.58 _ exchanged sillca Zinc Phosphate _ _ _ _ _ _ 4.26 Xylene/n-Butanol 10.08 10.4111.16 12.01 12~78 9.46 9.86 (1:1 volume 30 ratio) PART B
Versamid 115 2.11 1.18 2.33 2.51 2.89 1 a 98 2.06 curing agent for 35 the epoxy resin (ex Cray Valley Products Ltd) Xylene/n-butanol 40 (l:lvolume ratio 1.14 1.17 1.26 1.35 1.56 1.07 1.11 as solvent) ~ _ __ .
Pigment Volume 65 65 65 65 65 65 65 Concentration Specific Gravity 2.92 2.83 2.64 2.45 2.26 3.11 2.99 of liquid paint Vol~ replacement 10 15 25 35 45 0 10 50 of zinc dust _ ~
THIX0M~N, EPIKOTE, BENTONE, VERSAMID AND BEETLE are registered trade marks.
~ 25511~
Composition B is a typical zinc-rich epox~ coating composition of the type usually employed on new steel structures.
Compositlon C is an experimental cGmposition to determine whether the addition of zinc phosphate corro~ion inhibitor to B
improves performance.
Thixomen is a hydrogenated castor oil which acts as a thixotrope. Versamid 115 is a polyamide resin. Beetle BE640 is an n-butylated urea resin and is used as a flow control agent.
Part A of each composition was prepared by blending the resin3, solvent and thixotrope, heating to a temperature of about 35C for approximately 10 minutes and then dispersing the pigments in the gelled mixture using a high speed disperser.
Corrosion Test Parts A and B were mixed together and then applied eo standard degreased, polished mild steel panels. The paints were applied by spin coating except for Comparative Composition C which was applied with a brush. The coatings were scratched through to the bare metal and the panels sub~ected to tlle ASTM B117-73 salt spray test for 500 hours. The amount of white zinc corrosion deposits on the surface of the panels and the amount of underfilm corrosion oE the steel was assessed according to ASTM D 610-68 and the degree of blistering of the coatings was assessed according to ASTM D 714-56, The evaluation tests ASTM D 610-68 and ASTM D 714-56 are visual tests in which values are assigned on a scale of 0 to 10 where 10 is a good result i.e~ no corrosion or no bli~ters and 0 is a bad result i.e, 100 per cent of the surface corroded or very large blisters.
The results are given in Table 3 and show that the paints according to the present invention protected the mild steel panels better than either o the two comparative compositions. The amount of zinc corrosion depo3its was reduced as compared with the comparative compositions and the paints according to the invention were less prone to blistering. Somewhat surprisingly the best results were obtained with a paint in which 45% by volume of the zinc powder was replaced with the calcium exchanged silica corrosion inhibiting particles (Example 6).
~25~8~
Table 3 Result3 of Accelerated Weathering Tests (ASTM B117 - 73~
Coating Composition Average Dry Surfare Surface Underfilm Film Thickness Blistering Corrosion Corro~ion (um) Deposit~ of steel Examples
_ _ _ _ Epoxy resin6.166,37 6.83 7O358.23 5.79 6.03 (Epicote 1001X75 ex SHELI.) 15 Beetle BE 640 0.41 0.42 0.450.49 0.7 0.38 0.40 (ex BP Chemicals Limited) Thi~omen 0.34 0.35 0.37 0.40 _ 0.32 0.33 20 (ex ICI) Zlnc Dust77.6075.74 71O61 66.84 61,2681.00 75.95 Calclum- 2.16 3.36 5.99 9.0512.58 _ exchanged sillca Zinc Phosphate _ _ _ _ _ _ 4.26 Xylene/n-Butanol 10.08 10.4111.16 12.01 12~78 9.46 9.86 (1:1 volume 30 ratio) PART B
Versamid 115 2.11 1.18 2.33 2.51 2.89 1 a 98 2.06 curing agent for 35 the epoxy resin (ex Cray Valley Products Ltd) Xylene/n-butanol 40 (l:lvolume ratio 1.14 1.17 1.26 1.35 1.56 1.07 1.11 as solvent) ~ _ __ .
Pigment Volume 65 65 65 65 65 65 65 Concentration Specific Gravity 2.92 2.83 2.64 2.45 2.26 3.11 2.99 of liquid paint Vol~ replacement 10 15 25 35 45 0 10 50 of zinc dust _ ~
THIX0M~N, EPIKOTE, BENTONE, VERSAMID AND BEETLE are registered trade marks.
~ 25511~
Composition B is a typical zinc-rich epox~ coating composition of the type usually employed on new steel structures.
Compositlon C is an experimental cGmposition to determine whether the addition of zinc phosphate corro~ion inhibitor to B
improves performance.
Thixomen is a hydrogenated castor oil which acts as a thixotrope. Versamid 115 is a polyamide resin. Beetle BE640 is an n-butylated urea resin and is used as a flow control agent.
Part A of each composition was prepared by blending the resin3, solvent and thixotrope, heating to a temperature of about 35C for approximately 10 minutes and then dispersing the pigments in the gelled mixture using a high speed disperser.
Corrosion Test Parts A and B were mixed together and then applied eo standard degreased, polished mild steel panels. The paints were applied by spin coating except for Comparative Composition C which was applied with a brush. The coatings were scratched through to the bare metal and the panels sub~ected to tlle ASTM B117-73 salt spray test for 500 hours. The amount of white zinc corrosion deposits on the surface of the panels and the amount of underfilm corrosion oE the steel was assessed according to ASTM D 610-68 and the degree of blistering of the coatings was assessed according to ASTM D 714-56, The evaluation tests ASTM D 610-68 and ASTM D 714-56 are visual tests in which values are assigned on a scale of 0 to 10 where 10 is a good result i.e~ no corrosion or no bli~ters and 0 is a bad result i.e, 100 per cent of the surface corroded or very large blisters.
The results are given in Table 3 and show that the paints according to the present invention protected the mild steel panels better than either o the two comparative compositions. The amount of zinc corrosion depo3its was reduced as compared with the comparative compositions and the paints according to the invention were less prone to blistering. Somewhat surprisingly the best results were obtained with a paint in which 45% by volume of the zinc powder was replaced with the calcium exchanged silica corrosion inhibiting particles (Example 6).
~25~8~
Table 3 Result3 of Accelerated Weathering Tests (ASTM B117 - 73~
Coating Composition Average Dry Surfare Surface Underfilm Film Thickness Blistering Corrosion Corro~ion (um) Deposit~ of steel Examples
3 118 10 4 10
4 122 10 7 10 ~ 84 10 10 10 Comparative Composition I I I I _ J
The above rasults are on an exponential scaleO
Example 7 and Gomparison Examples 8 and 9 For comparison purposes ~inc-rich paint~ based upon an epoxy re~in (simllar formulatio~ to that in Example 2~ incorporating Barium Metaborate at two levels of substitu~ion (10 per cent and 20 per cent by volume) were prepared and tested against a zinc-rich paint in which 45 per cent of the zinc by volume was replaced by a calciu~/silica similar to that in Example 2. Formulatians are given in Table 6, and results of 800 hours ASTM salt spray test in Table The results show poor perfor~ance from Barium Metaborate (recommended for this application by the manufacturers) and a much better performance from calciu~/~illca at a higher level of substitution.
Comparison Example 10 and Examples 11 and 12 Zinc-rich paints based upon a chlorinated rubber binder were prepar~d incorporating calcium/silica (similar to the pig~ent in Example 2) at two levels of substitution of the ~inc (20 per cent ~L~5~
and 30 per cent by volu~e) and te~ted agalnst a zinc-rich paint without additives. Formulatlons are given in Table 7, and r~sults of 350 hours ASTM ~alt spray testing in Table 5. The re~ult~ show a marked lmprovement ln performance with increasing calcium/silica content, although ~he perfonman~e r~mains inferior to epoxy-based paints, due to the superior properties of the epoxy binder.
RESULTS OF ACCELERATED WEATHERING TEST
(ASTM B117-73 SALT SPRAY, 800 HOURS) ON FURTHER
_ Example or Replacement Average Dry Surface Result~ Underfilm Comparison of Film Stainingb Sub~trate Exa~ple Zinc v/v Thickness Blisteringa twhite ru~t) Corrsionb _ , 7 45% Ca/SiO2 107 10 7 9 8 10~ Busan 8~ 6D 2 2 9 20% Busan103 4D 4 6 . _ . _ __ _ a. A~sessment according to ASTM D714-56, where 10 3 good (no blis~ers), 0 ~ bad (very large blisters). Letter~
des~gnate frequency F - fewJ MD - ~edium - den~e, D - dense.
b. A~sessment according to ASTM D610-68, where 10 3 good (no corrosion), O - bad (100% corroded).
RESULTS OF ACÆI~R~T D WEATHERING TEST
(ASTM B117-73 SALT SPRAY, 350 HOURS) ON ZINC~RICH
CHLORINATED R _ ER PRIMERS INCORPORATING CALCIUM/SILICA
Example or Replacement Average nry Surface Resul~s Underfilm Comparison of Film Stalningb Substrate 35 Example Zinc v/v(um) Blisteringa (white rust) Corr9i~nb 11 19% Ca/Si258 6D 10 4 12 28% Ca/S102 65 8D 10 6 a. A3sessment according to ASTM D714-56~ wher~ 10 - good ~no blister~), o 8 bad (very large bllsters~. Letters designate frequency F - few, MD 3 medium - dense, D - dense.
b. As~e~sment according to ASTM D610-68, where 10 a good (no corrosion), 0 3 bad (100% corroded).
EXAMPL~ 7 - FURTHER EPOXY FORMWLA IONS PARTS BY WEIGHT
Ex~=ple ~x~ple Exa~ple _ _ __ PART A
Epicote 1001 x 75 6.30 6.59 8.34 Beetle BE o40 0.54 0.56 0072 EFKA-63 _ _ O.45 Zinc Dust 75.80 70.4859.78 Busan 11-M1 3~99 8.35 Calcium/Silica _ _ 13.00 Bentone SD-2 0.20 0.21 0.43 Xylene/Butanol 1:1 9.77 10.25 12.77 VerRamid 115 2,21 2.31 2.93 Xylene/Butanol 1:1 1,19 1,25 1.58 PVC% 65 65 64 Palnt Den~ity 2.96 2.82 2,23 Volume Solids %55 55 54.6 Vol % replacement of Zinc Dust 10 20 45 9~
Busa~ 11-Ml i9 a Bariu~ Met3borate pig~ent produced by Buckman Laborator~s Inc.
EFKA-63 is a wettlng and suspending agent supplied by Croxton and Garry.
Paints 8 and 9 were prepared ~imllarly to tho3e in ~anple 2;
for paint 7, part A was prepared by ball-millin~ all co~pone~t~
togPther excepting the zinc dust, which ~a~ subsequently added b~
Hlgh Speed Disperser.
In all ~a~es Par~s A and B were mi~ed together i~mediately prior ~o application.
TABL~ 7 EXA~PLES 10 TO 12 - CHLORINATED FUBB~R FORMULATIONS PARTS BY W~IGHT
_ _ 1O _ _ Alloprene*R10 4.09 5.57 6.29 20 Cereclor 70 2.70 3.67 4.15 Cereclor 42 1.39 1.89 2.14 Rheopla~*39 0~19 O,26 0.29 25 Zinc Du~t 74.51 70026 63.64 Calclum/Silica _ 4.67 7.27 30 Xylene 8.56 60 ô4 8.11 BP 180 8.56 6.84 8.11 PVC~ 65.3 61.6 59.4 Paint Den~ity 2.79 2.81 2.51 40 Volume Solids % 45.1 55~3 53.2 Vol ~ replacement of Zinc Dust O 19 28 _ _....... __ * trade marks 12 ~i ,~
In all cases all ingredients except the pigments were dissolved in tha solvents prior to lncorporation of the pigments. In paint lO
the zinc dust wa~ incorporated on a high speed disper~er; in paints ll and 12 the pigments were incorporated in a ball mill.
Alloprene R10 is a chlorinated rubber resin ~upplied by ICI.
Cereclor 70 i~ a chlorinated paraffin resin supplied by ICI, included as an inert extender.
Cereclor 42 i5 a chlorinated paraffin supplied by ICI~ includ2d as a plaætici~er.
~ is a stabili~er (epoxidised soya bean oil3 supplied by Ciba-Geigy.
The above rasults are on an exponential scaleO
Example 7 and Gomparison Examples 8 and 9 For comparison purposes ~inc-rich paint~ based upon an epoxy re~in (simllar formulatio~ to that in Example 2~ incorporating Barium Metaborate at two levels of substitu~ion (10 per cent and 20 per cent by volume) were prepared and tested against a zinc-rich paint in which 45 per cent of the zinc by volume was replaced by a calciu~/silica similar to that in Example 2. Formulatians are given in Table 6, and results of 800 hours ASTM salt spray test in Table The results show poor perfor~ance from Barium Metaborate (recommended for this application by the manufacturers) and a much better performance from calciu~/~illca at a higher level of substitution.
Comparison Example 10 and Examples 11 and 12 Zinc-rich paints based upon a chlorinated rubber binder were prepar~d incorporating calcium/silica (similar to the pig~ent in Example 2) at two levels of substitution of the ~inc (20 per cent ~L~5~
and 30 per cent by volu~e) and te~ted agalnst a zinc-rich paint without additives. Formulatlons are given in Table 7, and r~sults of 350 hours ASTM ~alt spray testing in Table 5. The re~ult~ show a marked lmprovement ln performance with increasing calcium/silica content, although ~he perfonman~e r~mains inferior to epoxy-based paints, due to the superior properties of the epoxy binder.
RESULTS OF ACCELERATED WEATHERING TEST
(ASTM B117-73 SALT SPRAY, 800 HOURS) ON FURTHER
_ Example or Replacement Average Dry Surface Result~ Underfilm Comparison of Film Stainingb Sub~trate Exa~ple Zinc v/v Thickness Blisteringa twhite ru~t) Corrsionb _ , 7 45% Ca/SiO2 107 10 7 9 8 10~ Busan 8~ 6D 2 2 9 20% Busan103 4D 4 6 . _ . _ __ _ a. A~sessment according to ASTM D714-56, where 10 3 good (no blis~ers), 0 ~ bad (very large blisters). Letter~
des~gnate frequency F - fewJ MD - ~edium - den~e, D - dense.
b. A~sessment according to ASTM D610-68, where 10 3 good (no corrosion), O - bad (100% corroded).
RESULTS OF ACÆI~R~T D WEATHERING TEST
(ASTM B117-73 SALT SPRAY, 350 HOURS) ON ZINC~RICH
CHLORINATED R _ ER PRIMERS INCORPORATING CALCIUM/SILICA
Example or Replacement Average nry Surface Resul~s Underfilm Comparison of Film Stalningb Substrate 35 Example Zinc v/v(um) Blisteringa (white rust) Corr9i~nb 11 19% Ca/Si258 6D 10 4 12 28% Ca/S102 65 8D 10 6 a. A3sessment according to ASTM D714-56~ wher~ 10 - good ~no blister~), o 8 bad (very large bllsters~. Letters designate frequency F - few, MD 3 medium - dense, D - dense.
b. As~e~sment according to ASTM D610-68, where 10 a good (no corrosion), 0 3 bad (100% corroded).
EXAMPL~ 7 - FURTHER EPOXY FORMWLA IONS PARTS BY WEIGHT
Ex~=ple ~x~ple Exa~ple _ _ __ PART A
Epicote 1001 x 75 6.30 6.59 8.34 Beetle BE o40 0.54 0.56 0072 EFKA-63 _ _ O.45 Zinc Dust 75.80 70.4859.78 Busan 11-M1 3~99 8.35 Calcium/Silica _ _ 13.00 Bentone SD-2 0.20 0.21 0.43 Xylene/Butanol 1:1 9.77 10.25 12.77 VerRamid 115 2,21 2.31 2.93 Xylene/Butanol 1:1 1,19 1,25 1.58 PVC% 65 65 64 Palnt Den~ity 2.96 2.82 2,23 Volume Solids %55 55 54.6 Vol % replacement of Zinc Dust 10 20 45 9~
Busa~ 11-Ml i9 a Bariu~ Met3borate pig~ent produced by Buckman Laborator~s Inc.
EFKA-63 is a wettlng and suspending agent supplied by Croxton and Garry.
Paints 8 and 9 were prepared ~imllarly to tho3e in ~anple 2;
for paint 7, part A was prepared by ball-millin~ all co~pone~t~
togPther excepting the zinc dust, which ~a~ subsequently added b~
Hlgh Speed Disperser.
In all ~a~es Par~s A and B were mi~ed together i~mediately prior ~o application.
TABL~ 7 EXA~PLES 10 TO 12 - CHLORINATED FUBB~R FORMULATIONS PARTS BY W~IGHT
_ _ 1O _ _ Alloprene*R10 4.09 5.57 6.29 20 Cereclor 70 2.70 3.67 4.15 Cereclor 42 1.39 1.89 2.14 Rheopla~*39 0~19 O,26 0.29 25 Zinc Du~t 74.51 70026 63.64 Calclum/Silica _ 4.67 7.27 30 Xylene 8.56 60 ô4 8.11 BP 180 8.56 6.84 8.11 PVC~ 65.3 61.6 59.4 Paint Den~ity 2.79 2.81 2.51 40 Volume Solids % 45.1 55~3 53.2 Vol ~ replacement of Zinc Dust O 19 28 _ _....... __ * trade marks 12 ~i ,~
In all cases all ingredients except the pigments were dissolved in tha solvents prior to lncorporation of the pigments. In paint lO
the zinc dust wa~ incorporated on a high speed disper~er; in paints ll and 12 the pigments were incorporated in a ball mill.
Alloprene R10 is a chlorinated rubber resin ~upplied by ICI.
Cereclor 70 i~ a chlorinated paraffin resin supplied by ICI, included as an inert extender.
Cereclor 42 i5 a chlorinated paraffin supplied by ICI~ includ2d as a plaætici~er.
~ is a stabili~er (epoxidised soya bean oil3 supplied by Ciba-Geigy.
Claims (4)
1 A composition suitable for the preparation of a surface protective coating composition by admixture with a binder, said composition comprising (i) elemental zinc in particulate form, (ii) inorganic oxide particles having corrosion inhibiting cations chemically bound to the surface thereof by ion exchange.
2 A composition as claimed in claim 1 wherein the amount of elemental zinc to ion exchanged inorganic oxide is from 75:1 to 3:1 by weight.
3 A composition as claimed in claim 1 wherein the inorganic oxide is silica and the corrosion inhibiting ions are calcium cations.
4 A coating composition suitable for application to a metal surface to inhibit corrosion which composition comprises:-(i) a binder, (ii) from 50 to 90% by weight of elemental zinc in particulate form based on the weight of the coating composition, and (iii) an effective amount of inorganic oxide particles having corrosion inhibiting ions chemically bound to the surface thereof by ion exchange.
5 A coating composition as claimed in claim 4 wherein the ratio of elemental zinc to ion exchanged inorganic oxide is from 75:1 to
3 A composition as claimed in claim 1 wherein the inorganic oxide is silica and the corrosion inhibiting ions are calcium cations.
4 A coating composition suitable for application to a metal surface to inhibit corrosion which composition comprises:-(i) a binder, (ii) from 50 to 90% by weight of elemental zinc in particulate form based on the weight of the coating composition, and (iii) an effective amount of inorganic oxide particles having corrosion inhibiting ions chemically bound to the surface thereof by ion exchange.
5 A coating composition as claimed in claim 4 wherein the ratio of elemental zinc to ion exchanged inorganic oxide is from 75:1 to
3:1 by weight.
6 A coating composition as claimed in claim 4 wherein the inorganic oxide is silica and the corrosion inhibiting ions are calcium cations.
7 A coating composition as claimed in claim 4 wherein the amount of corrosion inhibiting ions bound to the surface of the inorganic oxide is from 0.01 to 2.5 millimoles of corrosion inhibiting ion per gram of inorganic oxide.
8 A two part pack, the two parts of which on mixing form a coating composition as claimed in claim 4 further including a curable resin and a curing agent for the curable resin, the curable resin and curing agent being in different parts of the pack.
9 A paint suitable for the application to a metal surface to inhibit corrosion said paint comprising (i) a binder, (ii) from 50 to 90% by weight of elemental zinc in particulate form, and (iii) as corrosion inhibitor an effective amount of silica particles having calcium cations chemically bound to the surface thereof by ion exchange.
10 Ferrous metal structures coated with a composition as claimed in
6 A coating composition as claimed in claim 4 wherein the inorganic oxide is silica and the corrosion inhibiting ions are calcium cations.
7 A coating composition as claimed in claim 4 wherein the amount of corrosion inhibiting ions bound to the surface of the inorganic oxide is from 0.01 to 2.5 millimoles of corrosion inhibiting ion per gram of inorganic oxide.
8 A two part pack, the two parts of which on mixing form a coating composition as claimed in claim 4 further including a curable resin and a curing agent for the curable resin, the curable resin and curing agent being in different parts of the pack.
9 A paint suitable for the application to a metal surface to inhibit corrosion said paint comprising (i) a binder, (ii) from 50 to 90% by weight of elemental zinc in particulate form, and (iii) as corrosion inhibitor an effective amount of silica particles having calcium cations chemically bound to the surface thereof by ion exchange.
10 Ferrous metal structures coated with a composition as claimed in
claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB858508316A GB8508316D0 (en) | 1985-03-29 | 1985-03-29 | Corrosion inhibiting coating composition |
| GB8508316 | 1985-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1259184A true CA1259184A (en) | 1989-09-12 |
Family
ID=10576919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000505149A Expired CA1259184A (en) | 1985-03-29 | 1986-03-26 | Corrosion inhibiting coating compositions |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4643769A (en) |
| EP (1) | EP0196835B1 (en) |
| JP (1) | JPH0660295B2 (en) |
| CA (1) | CA1259184A (en) |
| DE (1) | DE3673205D1 (en) |
| DK (1) | DK166733B1 (en) |
| GB (1) | GB8508316D0 (en) |
| NO (1) | NO861066L (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8622465D0 (en) * | 1986-09-18 | 1986-10-22 | British Petroleum Co Plc | Corrosion inhibiting coating composition |
| GB8726157D0 (en) * | 1987-11-07 | 1987-12-09 | British Petroleum Co Plc | Corrosion-inhibiting composition |
| DE68908226T2 (en) * | 1988-03-31 | 1994-01-05 | Nippon Paint Co Ltd | Temporary rust-resistant coating compound. |
| US5246488A (en) * | 1988-03-31 | 1993-09-21 | Nippon Paint Co., Ltd. | Temporary rust resisting coating composition |
| DK0560785T3 (en) * | 1990-11-27 | 1996-08-12 | Sika Chemie Gmbh | Two-component epoxy resin-zinc dust primer for steel surfaces |
| JPH0815584B2 (en) * | 1990-11-30 | 1996-02-21 | 日本鋼管株式会社 | Weldable colored steel sheet |
| JP2844953B2 (en) * | 1991-03-29 | 1999-01-13 | 日本鋼管株式会社 | Weldable colored steel plate |
| US5858465A (en) * | 1993-03-24 | 1999-01-12 | Georgia Tech Research Corporation | Combustion chemical vapor deposition of phosphate films and coatings |
| AU709965B2 (en) * | 1994-10-21 | 1999-09-09 | Elisha Holding Llc | Corrosion preventing buffersystem for metal products |
| US6080334A (en) | 1994-10-21 | 2000-06-27 | Elisha Technologies Co Llc | Corrosion resistant buffer system for metal products |
| US6214473B1 (en) * | 1998-05-13 | 2001-04-10 | Andrew Tye Hunt | Corrosion-resistant multilayer coatings |
| US7244498B2 (en) * | 2002-06-12 | 2007-07-17 | Tda Research, Inc. | Nanoparticles modified with multiple organic acids |
| US6933046B1 (en) * | 2002-06-12 | 2005-08-23 | Tda Research, Inc. | Releasable corrosion inhibitor compositions |
| DE102006002545A1 (en) * | 2006-01-18 | 2007-07-19 | Ewald Dörken Ag | Silicon-based corrosion inhibitor |
| CN101918500B (en) | 2007-11-19 | 2015-05-20 | 格雷斯股份有限两合公司 | Submicron anti-corrosive particles |
| AR074508A1 (en) * | 2008-12-08 | 2011-01-19 | Grace Gmbh & Co Kg | ANTI-CORROSIVE PARTICLES |
| GB201706574D0 (en) | 2017-04-25 | 2017-06-07 | Univ Swansea | Corrosion inhibitor |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3849141A (en) * | 1972-10-18 | 1974-11-19 | Diamond Shamrock Corp | Pulverulent metal coating compositions |
| DE2637773A1 (en) * | 1975-08-28 | 1977-03-10 | Aaron Oken | High zinc content paint - with zinc dust suspended by reaction prod. of alkyl polysilicate and hydrated metal salt |
| GB2071070B (en) * | 1979-02-03 | 1983-02-02 | British Petroleum Co | Corrosion inhibitors method of producing them and protective coatings containing them |
| US4419137A (en) * | 1980-08-09 | 1983-12-06 | The British Petroleum Company Limited | Corrosion inhibitors, method of producing and protective coatings containing same |
| GB2091235B (en) * | 1981-01-10 | 1984-11-28 | British Petroleum Co | Method of producing corrosion inhibitors |
| ZA823625B (en) * | 1981-06-30 | 1983-12-28 | Elkem Metals | Zinc rich paint formulations employing manganomanganic oxide pigment |
| GB2122985A (en) * | 1982-02-16 | 1984-01-25 | Standard Telephones Cables Ltd | Corrosion inhibiting coatings |
| US4474607A (en) * | 1982-03-19 | 1984-10-02 | The British Petroleum Company P.L.C. | Method of inhibiting corrosion using cations |
-
1985
- 1985-03-29 GB GB858508316A patent/GB8508316D0/en active Pending
-
1986
- 1986-03-18 US US06/840,913 patent/US4643769A/en not_active Expired - Lifetime
- 1986-03-19 NO NO861066A patent/NO861066L/en unknown
- 1986-03-21 EP EP86302090A patent/EP0196835B1/en not_active Expired
- 1986-03-21 DE DE8686302090T patent/DE3673205D1/en not_active Expired - Lifetime
- 1986-03-26 DK DK145086A patent/DK166733B1/en not_active IP Right Cessation
- 1986-03-26 CA CA000505149A patent/CA1259184A/en not_active Expired
- 1986-03-28 JP JP61070625A patent/JPH0660295B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DK145086A (en) | 1986-09-30 |
| JPS61268772A (en) | 1986-11-28 |
| NO861066L (en) | 1986-09-30 |
| EP0196835B1 (en) | 1990-08-08 |
| US4643769A (en) | 1987-02-17 |
| EP0196835A2 (en) | 1986-10-08 |
| JPH0660295B2 (en) | 1994-08-10 |
| DE3673205D1 (en) | 1990-09-13 |
| DK166733B1 (en) | 1993-07-05 |
| EP0196835A3 (en) | 1988-03-09 |
| GB8508316D0 (en) | 1985-05-09 |
| DK145086D0 (en) | 1986-03-26 |
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